Copper containing disazodyestuffs



UNITED STATES PATENT OFFICE RICHARD STUSSER', OF COLOGNE-DEUIZ, AND KARL WIEDEMANN, OF COLOGNE-MUD HEIM, GERMANY, ASSIGNORS T GENERAL ANILINE WORKS, INC., OF NEW YQRK,

N. Y., A CORPORATION OF DELAWARE CQPPER CONTAINING DISAZODYESTUFFS No Drawing. Application filed March 6, 1931, Serial No. 520,639i, and in Germany March 11, 1930.

The present invention relates to a process of preparing copper compounds of d sazo dyestuils and to the new copper containing azodyestuffs obtainable thereby, more particularly it relatesto dyestufi's which may be represented by the probable general formula:

OH OH O H (mllaamm HOKS/ OH O.alk 0.811:

HOsS

wherein R stands for a naphthalene nucleus, 0 in which the hydroxy group stands in o-position to the azo bridge, alk stands for an alkyl group, such as methyl, ethyl or propyl, and wherein all nuclei may be further substituted for example, by halogen, alkyl, 0xalkyl, alkyloxy, the nitro group, the sulfonic acid group, the carboxyllc acid group, the hydroxy group and the amino group may be substituted by acyl or a hydrocarbon radical, with a compound of di-valent copper, yielding copper, such as cupric sulfate, cupric chloride, tetrammine cupric sulfate. The

temperature at which our process can be car-. ried out may be varied within the widest limits, say between about and (1., and the reaction is complete when the shade of the dyestufi no longer changes which can U NH: T

be determined by taking test portions and dyeing cotton with these test portions.

Our new copper containing azodyestuils are, in form of their alkali metal salts, generally dark powders, soluble in water with a blue coloration and dye cotton and viscose silk blue to violet shades of good fastness properties.

The invention is illustrated by the following examples, without being limited thereto:

Example 1.244 parts by weight of 4.4- diamino-3.3-dimethoxydiphenyl are tetrazotized with 138 parts by weight of sodium nitrite and 800 parts by weight of hydrochloric acid (19 B.), rendered alkaline with sodium bicarbonate and coupled with 304 parts by weight of l-hydroxynaphthalene-3.6-disulfonic acid. After completion of the formation of the intermediate product the mixture is rendered alkaline by means of sodium carbonate and a solution, rendered alkaline by means of sodium carbonate, of 344 parts by weight of 2-(p-methoxyphenyl-amino) 5-hydroxynaphthalene-7-sulfonic acid in water is added. Then 200 parts by weight of 0 H O H O H CGHLNH OaH HOaS 20 hours. The dyestufi' containing copper of the following formula:

OH OH is then filtered. dissolved in hot water, ten dered alkaline by means of sodium carbon- OH CcHsNHwsoaH ate, filtered, salted out from the filtrate and filtered. After drying a black powder is obtained, which dissolves in water with a blue coloration and dyes cotton, silk and viscose artificial silk blue shades, very fast to light and fast to alkalies.

When coppering in the same manner the azo-dyestufi' having in' its free state the following formula:

OCH; OCH;

CaH6.CO,NH SOaH there is obtained a copper compound having the same properties.

Example 2.-One molecular proportion of the dyestufl' obtained as described in Example 1 from one molecular proportion of 4.4'-diamino-3.3-dimethoxydiphenyl, one molecular proportion of 1-hydroxy-8-ethoxynaphthalene-3.6-disulfonic acid and one molecular proportion of Q-phehylamino-5-hydroxynaphthalene-7-sulfonic acid is boiled under a reflux for a prolonged period with two molecular proportions of copper sulfate in aqueous solution rendered weakly acid to Congo, until the shade no longer changes.

The working up then follows as in Example 1. A black powder is thus obtained which dissolves in water with a blue coloration and which dyes cotton, silk and viscose artificial silk blue shades, fast to light. In its free state the dyestu'fi has the probable formula:

OaH v When coppering in the same manner the Tom azo-dyestuff having in its free state the following formula:

there is obtained a copper compound having the same properties.

Example 3.One molecular proportion of the disazodyestufl obtained as described in Example 1 from one molecular proportion of tetrazotized 4.4-diamino-3.3-dimethoxydiphenyl, one molecular proportion of 8-chloro- 1-naphthol-3.6-disulfonic acid and one molecular proportion of 2-benzoylamino-5-hydroxynaphthalene 7-sulfonio acid is heated for about 2 hours in aqueous ammoniacal solution with 2 molecular proportions of tetramine cupric sulfate in the presence of free ammonia at a temperature of 7080 C. The copper containing dyestufi' thus obtained dyes cotton and viscous reddish-blue shades Y J-SOaH fast to light. In its free state it has the probable formula:

Cl OH OH \Ve claim:

1. The process which com prises heating a water soluble salt of an azodyestuli' of the general formula:

HOaS

group consisting othalogen, alkyl, oxalkyl, alky ox the nitro group, the sulfonic acid sl' bstituted by acyl or a hydrocarbon radical, in. aqueous solution with two molecular prowherein R stands for a naphthalene nucleus in which the hydroxygroup stands in o-position to the azo bridge, alk stands for an alkyl group and wherein all nuclei may be further substituted by substituents of the group consisting of halogen, alkyl, oxalkyl,

HO S

. molecular proportion of an alkali metal salt of an azo-dyestufi of the general formula:

0 CH3 0 CH3 Call 11038 OCHa in weak aqueous acid solution with the addition of two molecular proportions of copper sulfate at a temperature of 110115 (1., until the shade of the dyestufi' no longer changes.

41 The process which comprises boiling one molecular proportion of an alkali metal salt O-alk o-alk OH on 1 I NHa wherein R stands for a naphthalene nucleus of the dyestufi mom on OOH; ou: on

HOaS -SOaH HOaS NHCuH5 in which the hydroxy group stands in o-position to the azo bridge, alk stands for an alkyl group and wherein all nuclei may be further substituted by substituents of the in aqueous solution reacting weakly acid containing two molecular proportions of copper sulfate, until the shade of the dyestufi no longer changes.

5. The process which comprises heating ter with a blue coloration and dyeing cotton one molecular proportion of the sodium salt blue to violet shades of good fastness propof the dyestuff: erties.

01 on com OOH; on

H015 01H HO|S H-CO-C|H| for about 2 hours in aqueous ammoniacal solution containing 2 molecular proporgl g gg gg ig i figm contammg tions of tetrammine cupric sulfate and a p p on on on on H018 0,11 l HOaS- NH CHI Cu,

small quantity'of free ammonia at a temperature of -80 C.

6. As new products copper containing azo-compounds of the probable general formula:

being a black powder, soluble in Water with a blue coloration and dyeing cotton, silk and viscose artificial silk blue shades, very fast to light and fast to alkalies.

O H OH OH HOaS- wherein R stands for a naphthalene nucleus 8. As a new product a copper containing in WhlCh the hydroxy group stands in o-posiazo-compound of the probable formula:

no on on Ho1s- SO;H HOiS NH'CGHB being a black powder, solublein water, dyeing cotton, fsilk and viscose artificial silk blue shades ast to li ht.

th halogenthalky 9 As a iiewprodu ct a copper containing 8 In To group 6 Sn azo-compound of the formula:

tion to the azo bridge, and wherein all nuclei may be further substituted by substituents of the group consisting of oxalkyl, alkyloxy,

01 OH OH OH OH m H013 SOaH HOaS NH to (gab IJ-Cuz fonic acid group, the carboxylic acid group, being a dark owder and dyeing cotton and the hydroxy group, and the amino group may viscose reddis -blue shades fast to light. be substituted by acyl or a hydrocarbon In testlmony w We our slgna radical, being in form of their alkali metal tures. RICHARD STUSSER. salts generally dark powders, soluble in Wa- KARL WIEDEMANN. 

